Development of silver halide photographic materials

ABSTRACT

A METHOD FOR THE DEVELOPMENT OF SILVER HALIDE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS, WHICH COMPRISES DEVELOPING A SILVER HALIDE PHOTOGRAPHIC MATERIAL IN THE PRESENCE OF A COMPOUND REPRESENTED BY THE FOLLOWING GENERAL FORMULA   R-O-(CH2-CH(-O-CH2-CH(-OH)-CH2-N+&lt;(-Z-))-CH2-O)X-(CH2-   CH(-OH)-CH2-O)Y-H. X X(-)   IN WHICH R IS SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM AND R&#39;&#39;CO-, WHEREIN R&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, AN ALKYL GROUP, A SUBSTITUTED ALKYL GROUP, AN ARYL GROUP AND A SUBSTITUTED ARYL GROUP, WHEREIN X+Y IS A NUMBER RANGING FROM 3 TO 50, X REPRESENTS AN ANION, AND Z REPRESENTS AN ATOMIC GROUP NECESSARY FOR COMPLETING A HETEROCYCLIC RING, IS DISCLOSED.

United States Patent ()1 hce 3,671,247 Patented June 20, 1972 Int. 01. G03c 5/30 US. Cl. 96-663 9 Claims ABSTRACT OF THE DISCLOSURE A method for the development of silver halide photographic light-sensitive materials, which comprises developing a silver halide photographic material in the presence of a compound represented by the following general formula in which R is selected from the group consisting of a hydrogen atom and RCO--, wherein R' is selected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group, wherein x+y is a number ranging from 3 to 50, X represents an anion, and Z represents an atomic group necessary for completing a heterocyclic ring, is disclosed.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to a method for the development of silver halide photographic light-sensitive materials.

(2) Description of the prior art 'It has been desired in the development of silver halide photographic light-sensitive materials to accelerate the rate of development and to increase the sensitivity of the developed light-sensitive material. For this purpose, it is well known to add an amine compound to a developer as a development accelerator. However, many amine compounds are volatile and have generally a bad odor. It is difiicult to keep the concentration of the developing solution at a consistant level. The handling thereof is sometimes rather tedious because of the poisonous characteristics. Addition of such amine compounds to a developer accelerates the rate of development but does not affect the sensitivity and is accompanied by an increase in fog, a generation of scum and a deterioration of the granularity of the developed silver.

In addition, it is known that a quaternary salt compound is capable of accelerating development (as disclosed in T. H. James, Phot. Sci. Tech., 19B, 53 (1953)) and a quaternary salt compound is actually added to a developer or an emulsion for this purpose (as disclosed in US. Pats. 2,940,851 and 3,129,100). The quaternary salt compounds of the prior art have an excellent development accelerating efifect as Well as excellent sensitivity increasing effect, but they usually increase fog, as well,

It is a principal object of the invention to provide a method of developing silver halide photographic lightsensitive materials using a development accelerator which is free from the disadvantages described above.

SUMMARY OF THE INVENTION The above-described object of the invention can be accomplished by developing a silver halide photographic light-sensitive material in the presence of a compound represented by the following general formula ROCH CHCH2O)I(CH:CHCH O)yH-IX- H of. OCHzfiIHCHzN Z 0H in which R represents a hydrogen atom or R'CO-, wherein R is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, x+y is a number of from 3 to 50, X represents an anion and Z represents an atomic group necessary for forming a heterocyclic ring.

DETAILED DESCRIPTION OF THE INVENTION The compounds represented by the above-described general formula are characterized as having the OH group in the 5 position to the N+. These compounds not only accelerate the rate of development and increase the sensitivity of a silver halide photographic light-sensitive material, but also do not produce as much fog in the developed photographic material and also they do not deteriorate the granularity of the developed image.

Suitable alkyl groups for R in the above-described formula are those alkyl groups having less than 12 carbon atoms, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl and dodecyl groups. Suitable substituted alkyl groups are halogenated alkyl groups such as chloromethyl, bromopropyl and the like. Suitable aryl and substituted aryl groups are phenyl and carboxyphenyl groups. Preferably R is hydrogen.

x-i-y in the above described formula ranges from 3 to 30, preferably from 20 to 50. A suitable ratio of x-l-y is from 1:1 to 1:5.

Specific examples of the compound of the invention, represented by the above-described formula, are:

Compound 1:

l 69 CHaiHCH:

onmncmfik H NH x:y=1:2; x+y=27.

Compound 10: In compound 9, x:y=1:1 and x+y=27. Compound 11:

i e oomoncnmi omonorg en x:y=1:1; x+y=27. Compound 13:

CnHnOHCOOH OH H 000 (CH CHCH O)x(CH CHCHz)UHICI" l e CHzZHCHz x:y=1:2; x+y=40. Compound 14:

x:y=1:1; x+y=50. Compound x:y=1:1; x+y=40.

These compounds can be synthesized generally by the following procedures.

Synthesis of Compound 4 To 1 mol of polyglycerine (molecular weight: 2000) is added stannic chloride as a catalyst and heated at 85 95 C. 1 mol of epichlorohydrin is added dropwise thereto with stirring and after the dropwise addition, the mixture is further stirred for 6 hours at 120 C. The unreacted epichlorohydrin is removed under reduced pressure and the residual solution is mixed with a small amount of water and washed with ether. After separating the aqueous phase, water is distilled off under reduced pressure. A large excess of pyridine is added to the residual solution and refluxed for 6 hours to obtain two separate layers. The lower layer is separated from which the excess pyridine is distilled off and then washed with ether to thus obtain the desired compound.

Synthesis of polyglycerine and its ester can be carried out according to the methods described in Kogyo Kagaku Zasshi (Industrial Chemistry Journal), vol. 68, pages 2101-2106 and Japanese Pat. No. 21,048/68.

The synthesis method described in Kogyo Kagaku Zasshi, vol. 68, is as follows:

To 1 mol of glycerine is added 0.02-0.04 mol of pulverized caustic soda and heated at ISO-160 C., to which a predetermined amount of glycidol is added dropwise with stirring. After the dropwise addition, the reaction is continued until no heat of reaction is evolved. \After the reaction, the reaction solution is neutralized with an aqueous solution of hydrochloric acid, dehydrated completely under reduced pressure and filtered to obtain the poly glycerine.

Polyglycerine ester is obtained by mixing polyglycerine with a fatty acid in a proportion of 1:1 and heated for esterification at 230 C. with caustic soda as a catalyst.

The synthesis method described in Japanese Pat. No. 21,048/68 is as follows:

Epichlorohydrin is hydrolized with an aqueous solution of an alkali metal hydroxide having a concentration of 6 to 50% at a temperature of 50 to 150 C. and a pH of 12 or greater to give the polyglycerine. When this hydrolyized polyglycerine is mixed with an organic acid and heated for esterification, a polyglycerine ester is obtained.

Synthesis of Compound 6 To 1 mol of polyglycerine (molecular weight: 2000) is added boron tritfluoride etherate as a catalyst and heated at -95 C. 1 mol of epichlorohydrin is added dropwise thereto with stirring and after the dropwise addition, the mixture is further stirred at C. for 8 hours. The unreacted epichlorohydrin is removed under reduced pressure and the residual solution is mixed with a small amount of water and washed twice with ether. After separating the aqueous phase, water is distilled oif under reduced pressure. A large excess of pyridine is added to the residual solution and refluxed for 16 hours to obtain two separate layers. The lower layer is separated from which the excess pyridine is distilled off and then washed with ether to thus obtain the desired compound.

Synthesis of Compound 9 To the reaction product of epichlorohydrin and polyglycerine synthesized by the method shown in the synthesis of Compound 4 is added a little excess of 2-methylimidazole and refluxed for 15 hours using methanol as a uniform solvent. After distilling off the methanol, the washing is repeated with acetone and ethyl acetate to give the desired compound.

The other compounds can be synthesized in a similar method to those described above.

The compound of the invention is applicable to silver halide photographic light-sensitive materials in general, for example, black-and-white positive type photographic light-sensitive materials of relatively low sensitivity, blackand-white negative type photographic light-sensitive materials of high sensitivity, photographic light-sensitive materials for X-ray and color photographic light-sensitive materials.

The compounds of the invention have an excellent development accelerating and sensitivity increasing effect unaccompanied by an increase in fog, whereas the wellknown amine compounds and quaternary salt compounds have the disadvantage that fog is increased in spite of their excellent development accelerating and sensitivity increasing effects.

The developers for which the method of the present invention is applied are conventional silver halide photographic developers, for example, aqueous alkaline solutions containing one or more of the developing materials such as hydroquinone, 1-phenyl-3-pyrozolidone, N- rnethyl-p-aminophenol and N,N diethyl-p-phenylenediamine. In addition, preservatives such as sodium sulfite, ascorbic acid or hydroxylamine, salts such as sodium sulfate, pH adjusting or buffering agents such as boric acid, borax, sodium hydroxide, sodium carbonate or sodium phosphate, development retarders such as potassium bromide or potassium iodide and organic anti-fogging agents such as 6-nitrobenzimidazole, benztriazole, benztriazole or 1-phenyl-S-mercaptotetrazole can be added thereto. Occasionally an organic solvent such as triethylene glycol or hexylene glycol and an aldehyde such as formalin or glutaraldehyde can be added. The known development accelerators such as amines and polyethylene glycols can also be used in combination.

The compounds of the present invention can be effectively incorporated in a developing solution such as a developer or a bath, preceding to the development and/ or in a silver halide emulsion. A satisfactory result is obtainable, in most cases, by use of one of the compounds of the present invention, though, in certain cases, an advantageous effect can be obtained by the combined use of two or more of the compounds. In the case of incorpo rating the compound of the invention in a developer, the amount incorporated generally ranges from 0.01 to 20 .g.

TABLE 1 DevelopedSminutes Time necessary for obtaining Amount Relative rel. sensitivity of Compound added (g./l.) sensitivity Fog Gamma 100, minutes Control 100 0. 04 1.70 8 Compound 4- 1 170 0.05 2.10 P 4. Compound 17 1 160 0.12 2.02 5

1 Compound 17:

(CH:)3 2C1 per 1 liter of the developer, most effectively from 0.1 to EXAMPLE 2 g. depending on the composition and properties of the developer. In the case of incorporation into a silver halide emulsion, the amount ranges generally from 0.1 to 200 g. per 1 mol of silver halide depending on the composition of the silver halide emulsion as well as the sensitizing method used. In this case, it can be incorporated in any stage of the emulsion making process and A commercial high speed film comprising a spectrally sensitized silver iodobromide gelatin emulsion was exposed using a sensitometer and then developed at 20 C. with a developer of the following composition.

most favorably, after the second ageing and before coat ing. Instead of incorporation directly in an emulsion layer, it can be added to an adjacent layer, such as a protective layer. Illustrative of the silver halide, emulsions used in the invention are silver chloride, silver bromide, silver chlorobromide, silver iodide, silver'iodobromide and silver chloroiodobromide emulsions. The emulsion can be chemically sensitized using an unstable sulfur compound and/or a gold compound. The emulsion can be spectrally sensitized using a cyanine dye or merocyanine dye. The emulsion can be stabilized using a heterocyclic compound, such as 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene or l-phenyl-S-mercaptotetrazole. The emulsion can be hardened using known hardeners such as, e.g., formalin or mucochloric acid and can contain a surface Water ml 800 l-phenyl-B-pyrazolidone g 0.2 Sodium sulfite g 100 Hydroquinone g-.. 5 Borax g 2 Boric acid g 1 Potassium bromide ..g 1

Water to make, 1000 ml.

1 Compound 18:

active agent for ease in coating. Moreover, a color coupler can be incorporated therein capable of forming a dye image through reaction with the oxidation product of a developing agent of an aromatic primary amine.

The following examples are to illustrate the invention in detail without limiting it.

EXAMPLE 1 A fine grain positive film for movie use comprising a fine grain silver chloroiodobromide-gelatin emulsion was exposed using a sensitometer and developed at 20 C. with a developer having the following composition.

Water ml 800 N-methyl-p-amiuophenol sulfate g 1.7 Sodium sulfite g Hydroquinone g 4.4 Borax 10 Potassium bromide g 0.5 Water to make, 1000 ml.

The compound of the invention, Compound 4, gave a higher sensitivity with less fog as is evident from the results.

EXAMPLE 3 A silver iodobromide gelatin non-spectrally sensitized emulsion was exposed using a sensitometer and then developed at 20 C. with a developer of the following composition.

Water ml 800 Sodium sulfite g 50 Sodium carbonate monohydrate g 23.4 Hydroquinone a 44 Potassium bromide g 0.5

Water to 1000 ml.

When the development was carried out for 8 minutes using this developer, the photographic characteristics shown in Table 3 were obtained. There are further shown the photographic characteristics in Table 3 in cases where the compounds of the invention (Compounds 9 and 10) and the known quaternary salt compound (Compound 19) were added.

TABLE 3 Characteristics Amount added Relative Compound (g./l.) sensitivity Fog Gamma Control 100 0 18 0.68 Compound 9. 1 160 0 l9 0. 88 Compound 1 150 0 19 0. 85 Compound 19 1 105 0.45 0.7 1

1 Compound 19:

As is evident from these results, the compound of the invention gives a higher sensitivity without an increase of fog. As compared with Compound 19 outside the scope of the invention, the compound of the present invention gives rise to better effects, that is, less fog and a higher sensitivity and gamma.

EXAMPLE 4 Compounds 5, 6 and 11 of the invention in the form of an aqueous solution were respectively added to a silver iodobromide gelatin emulsion containing 3.0% by mol of silver iodide and coated onto a film base followed by drying. Test films thereof were exposed using a sensitometer and then developed at C. for 8 minutes with the developer of Example 1 to obtain the photographic characteristics shown in Table 4.

What is claimed is:

1. A method for the development of silver halide photographic light-sensitive materials, which comprises developing a silver halide photographic material in the presence of a compound represented by the following general formula in which R is selected from the group consisting of a hydrogen atom and R'CO--, wherein R' is selected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group, wherein x+y is a number ranging from 3 to 50, X represents an anion, and X represents an atomic group necessary for completing a heterocyclic ring.

2. The method as claimed in claim 1, wherein said compound is incorporated into a developer.

3. The method as claimed in claim 1, wherein said compound is incorporated into a silver halide photographic material.

4. The method as claimed in claim 1, wherein said compound is 8 wherein xzy is substantially 1:5, and x+y is substantially 27.

5. The method as claimed in claim 1, wherein said compound is HO(CHQCHCHzO)r(CH CHCHzOMH-zClwherein xzy is substantially 1:2 and .x+y is substantially 27.

6. The method as claimed in claim 1, wherein said compound is HO (CHzCHGHzO)1(CHzCHCH OM H-1Cl G9 OOHA JHCHZ i wherein xzy is substantially 1:1 and x+y is substantially 27.

7. The method as claimed in claim 1, wherein said compound is HO(CH2OHOH2O)Z(CH2$HCH2O)IIH-$C1 H NH wvherein x:y is substantially 1:2 and x+y is substantially 27.

8. The method as claimed in claim 1, wherein said compound is selected from the group consisting of H wherein any is 1:2 and x+y is 40, and

CHCOOH CHCO0(OH2OHGH20)Z(OH3?HCH20)I/HIC1 e/ oomonornrp I on \TNH wherein x:y is 1:1 and x+y is 27,

C H CHCOOH CHzCOC(CHzCHCHQO)I(CHzCHCH20)j/H-ZEC1 9 10 wherein xzy is 1:2 and x+y is 40, and References Cited CHCOOH UNITED STATES PATENTS g C C oymo c c ow c et a1 1 3,471,297 10/1969 Sprung 9666.3 5 3,129,100 4/1964 Grabhofer et a1. 9695 GB f I NORMAN G. TORCHIN, Primary Examiner 0H E. C. KIMLIN, Assistant Examiner wherein x1 is 1:1 and x-l-y is 50,

is incorporated into a silver halide emulsion layer of said 96 95 photographic material.

US. Cl. X.R. 

